Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J3/00—Processes of treating or compounding macromolecular substances
  • C08J3/20—Compounding polymers with additives, e.g. colouring
  • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/28—Nitrogen-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
  • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
  • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2427/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
  • C08J2427/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
  • C08J2427/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
  • C08J2427/18—Homopolymers or copolymers of tetrafluoroethylene
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
  • C08K3/20—Oxides; Hydroxides
  • C08K3/22—Oxides; Hydroxides of metals
  • C08K2003/2258—Oxides; Hydroxides of metals of tungsten
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/16—Applications used for films
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2310/00—Masterbatches

Definitions

• This invention relates to polymeric materials and particularly, although not exclusively, relates to fluoropolymer, for example ethylene tetrafluoroethylene (ETFE), films.
• fluoropolymer for example ethylene tetrafluoroethylene (ETFE)
• ETFE films in architectural applications (e.g. for roofs, walls or windows of buildings) due to its high strength and self-cleaning properties.
• IR infra-red
• This problem may be addressed by providing air-conditioning units inside of the building to cool the air therein.
• attempts may be made to attenuate the IR radiation and/or reduce its transmission through ETFE films.
• any means used to attenuate IR radiation does not significantly attenuate passage of visible light.
• any means to attenuate radiation should not detrimentally affect the physical properties of the film or its low energy surface which leads to its self-cleaning properties.
• the aforementioned competing problems are challenging to solve in a way which is a cost-effective and practical.
• a film comprising a polymeric material (A) and an additive, wherein said polymeric material (A) is a fluoropolymer and said additive is selected from titanium nitride and tungsten oxide.
• Said film preferably comprises one or more thermoplastic polymeric materials and said additive, wherein at least one thermoplastic polymeric material in said film is said polymeric material (A).
• the ratio defined as the wt% of polymeric material (A) in said film divided by the total wt% of all thermoplastic polymeric materials in said film is suitably at least 0.5, preferably at least 0.75, more preferably at least 0.9, especially at least 0.95.
• the ratio defined as the wt% of fluoropolymers (e.g. having a repeat unit of Formula I as hereinafter described) in said film divided by the total wt% of all thermoplastic polymeric materials in said film is suitably at least 0.5, preferably at least 0.75, more preferably at least 0.9, especially at least 0.95. Particles of said additive preferably do not protrude from a matrix defined, at least in part, by said polymeric material (A).
• Said film suitably comprises at least 50 wt%, preferably at least 75 wt%, more preferably at least 90 wt%, especially at least 95 wt% of said polymeric material (A).
• Said film may comprise 80 to 120 parts by weight (pbw) of said polymeric material (A) and 0.2 to 5 pbw of said additive.
• a ratio defined as the wt% of said polymeric material (A) divided by the wt% of said additive may be in the range 10-1110, preferably in the range 20 to 700.
• Said film may include at least 0.1 wt%, preferably at least 0.2 wt%, of said additive. It may include less than 3 wt% or less than 2 wt% of said additive.
• Said film may have a thickness of at least 10 ⁇ , preferably at least 100 ⁇ or, more preferably, at least 150 ⁇ .
• the thickness may be less than 1000 ⁇ , preferably less than 500 ⁇ , more preferably less than 350 ⁇ .
• Said polymeric material (A) is preferably a thermoplastic polymer. It is preferably saturated. Polymeric material (A) preferably includes a repeat unit (XI) which includes a moiety
• said repeat unit (XI) is an ethylene repeat unit.
• Said polymeric material (A) preferably includes a repeat unit (XII) which includes a moiety
• Said repeat unit (XI) may be a part of said repeat unit (XII).
• Said polymeric material (A) preferably includes a repeat unit (XIII) which includes a moiety F X
• X is a halogen atom, preferably selected from a chlorine and a fluorine atom.
• X represents a fluorine atom.
• Said polymeric material (A) preferably includes a repeat unit (XIV) which includes a moiety
• X is as described above.
• X represents a fluorine atom.
• Said polymeric material (A) is preferably a copolymer which includes a repeat unit of formula I and a repeat unit of formula III.
• the ratio of the mol% of moieties III divided by the mol% of moieties I is suitably in the range 0.25 to 4, preferably in the range 0.6 to 1 .5, more preferably in the range 0.9 to 1 .1 .
• Said polymeric material (A) may include at least 60 wt% of moieties of Formula III; and it may include less than 90 wt% of moieties of Formula III.
• Said polymeric material (A) may include at least 10 wt% of moieties of Formula I; and it may include less than 40 wt% of moieties of Formula I.
• Said polymeric material (A) may include at least 60 wt%, preferably at least 80 wt%, more preferably at least 95 wt%, especially at least 99 wt% of moieties of Formula IV.
• Said polymeric material (A) may be ethylene chlorotrifluoroethylene (ECTFE) or an ethylene-tetrafluoroethylene copolymer (ETFE).
• Said polymeric material (A) may have a specific gravity by DIN EN ISO 12086 in the range 1 .5 to 1 .9 g/cm 3 .
• Said polymeric material (A) may have a melt flow index (297°C/5kg) by DIN EN ISO 1 133 in the range 7-13 g/1 Omins.
• Said polymeric material (A) may have a melting point by DIN EN ISO 12086 of at least 220°C, preferably at least 240°C, more preferably at least 260°C.
• the melting point may be less than 300°C, preferably less than 280°C.
• Said polymeric material (A) may have a tensile strength at break (23°C) by DIN EN ISO 527-1 of at least 40 MPa, preferably at least 47 MPa. It may be less than 70 MPa.
• Said polymeric material (A) may have an elongation at break (23°C) by DIN EN ISO 527-1 of at least 350%, preferably at least 430%. It may be less than 600%.
• Said polymeric material (A) may have a tensile modulus by DIN EN ISO 527-1 of at least 900 MPa, preferably at least 1 100 MPa. It may be less than 1500 MPa.
• Said polymeric material (A) may have a tear propagation resistance by DIN 53363 of at least 350 N/mm, preferably at least 450 N/mm. It may be less than 700 N/mm. Said polymeric material (A) may have a light transmission at 550nm based on a pure
• Said film could include a polymeric material (B) which is preferably a fluorpolymer.
• Polymeric material (B) is preferably a thermoplastic polymer. It is preferably saturated.
• Polymeric material (B) may have any feature of polymeric material (A) described. Thus, it may include moiety I, moiety II, moiety III and/or moiety IV; it is preferably an ethylene- tetrafluoroethylene copolymer (ETFE).
• EFE ethylene- tetrafluoroethylene copolymer
• polymeric materials (A) and (B) include the same types of repeat units.
• the ratio of the mol% of moieties I II divided by the mol% of moieties I is suitably in the range 0.25 to 4, preferably in the range 0.6 to 1 .5, more preferably in the range 0.9 to 1 .1 .
• Said polymeric material (B) may include at least 60 wt% of moieties of Formula III; and it may include less than 90 wt% of moieties of Formula III.
• Said polymeric material (B) may include at least 10 wt% of moieties of Formula I; and it may include less than 40 wt% of moieties of Formula I.
• Said polymeric material (B) may include at least 60 wt%, preferably at least 80 wt%, more preferably at least 95 wt%, especially at least 99 wt% of moieties of Formula IV.
• Polymeric material (B) preferably has specific gravity, melt flow index, melting point, tensile strength, tensile modulus, tear propagation resistance and light transmission as described for said polymeric material (A).
• polymeric materials (A) and (B) are preferably the same polymeric materials or are very similar.
• polymeric material (A) makes up at least 60 wt%, more preferably at least 80 wt%, especially at least 85 wt% of the total wt% of thermoplastic polymeric materials included in said film.
• polymeric material (A) makes up 90 to 100wt%, preferably 95 to 100 wt%, of the total wt% of thermoplastic polymeric materials in said film.
• the total wt% of thermoplastic polymeric materials included in said film may be made up of 5-15 wt% of polymeric material (B).
• the total amount of thermoplastic polymeric materials included in said film is made up of 80 to 100 wt% of polymeric material (A) and 0 to 20 wt% of polymeric material (B).
• An example of inclusion of a polymeric material (B) is when the C88AXMB polymeric material is used as described in Example 4.
• the sum of the wt% of all thermoplastic polymeric materials in the film and said additive is suitably at least 95 wt%, preferably at least 97 wt%, more preferably at least 99 wt%.
• thermoplastic polymeric materials titanium nitride and tungsten oxide in the film is suitably at least 95 wt%, preferably at least 97 wt%, more preferably at least 99 wt%.
• the sum of the wt% of polymeric material (A) and said additive is preferably at least 80 wt%, more preferably at least 90 wt%.
• the sum of the wt% of polymeric material (A), polymeric material (B) and said additive is preferably at least 95 wt%, preferably at least 97 wt%, more preferably at least 99 wt%.
• Said film may include at least 50 parts per million (ppm), for example at least 85ppm of said additive. Said film may include less than 5000ppm or less than 3000ppm of said additive.
• said additive is titanium nitride
• the sum of the wt% of polymeric material (A), and said titanium nitride is preferably at least 80 wt%, more preferably at least 90 wt%.
• the sum of the wt% of polymeric material (A), polymeric material (B) and said titanium nitride is preferably at least 95 wt%, preferably at least 97 wt%, more preferably at least 99 wt%.
• said film may include at least 50ppm, for example at least 85ppm titanium nitride. Said film may include less than 500ppm or less than 350ppm titanium nitride.
• said additive is tungsten oxide
• the sum of the wt% of polymeric material (A), and said tungsten oxide is preferably at least 80 wt%, more preferably at least 90 wt%.
• the sum of the wt% of polymeric material (A), polymeric material (B) and said tungsten oxide is preferably at least 95 wt%, preferably at least 97 wt%, more preferably at least 99 wt%.
• said film may include at least 250ppm, preferably at least 500ppm tungsten oxide. It may include less than 5000ppm or less than 3000ppm tungsten oxide.
• said additive is dispersed in the film. It is preferably dispersed throughout the film.
• Said film preferably comprises (especially consists essentially of) a homogenous mixture of said thermoplastic polymeric material (which includes polymeric material (A) and said additive).
• Said additive is preferably in the form of particles which are dispersed throughout said film and/or in said polymeric material (A).
• Particles of said additive in said film suitably have a d 50 of less than 50 ⁇ , preferably less than 25 ⁇ , more preferably less than ⁇ ⁇ and, especially, 5 ⁇ or less.
• said particles may have a d 50 of less than 2 ⁇ .
• the d 50 of said particles may be greater than 10nm, for example greater than 20nm.
• the d 50 may be measured by Laser Diffraction as described herein.
• less than 5 vol%, less than 3 vol% or less than 1 vol% of said particles have a particle size measured as described herein of more than 10 ⁇ or more than 5 ⁇ .
• less than 5 vol% of said particles have a particle size of more than 5 ⁇ .
• more than 5 vol%, preferably more than 25 vol%, more preferably more than 50 vol%, especially more than 75 vol% of said particles have a particle size of more than 20nm.
• the particle size distribution may be expressed by "span (S)," where S is calculated by the following equation: where d 90 represents a particle size in which 90% of the volume is composed of particles having a smaller diameter than the stated d 90 ; and d 0 represents a particle size in which 10% of the volume is composed of particles having a diameter smaller than the stated d 0 ; and d 50 represents a particle size in which 50% of the volume is composed of particles having a diameter larger than the stated d 50 value, and 50% of the volume is composed of particles having a diameter smaller than the stated d 50 value.
• Particle size distributions of particles in which the span (S) is from 0.01 to 10, or from 0.01 to 5, or from 0.1 to 3, for example, may be preferred.
• a size-ratio (SR) may be defined as:
• SR is suitably at least 5, is preferably at least 7, is more preferably at least 8 and, especially is at least 9. It may be less than 100 or less than 40.
• M
• Titanium nitride is known for having a stoichiometry in the range TiN 0 .
• said additive is titanium nitride
• said titanium nitride in said film preferably includes at least 74 wt%, preferably at least 77 wt% of titanium moieties
• Said titanium nitride in said film preferably includes less than 90 wt%, preferably less than 80 wt% of titanium moieties.
• Said titanium nitride in said film preferably includes at least 10 wt%, more preferably at least 20 wt% of nitrogen moieties.
• Said titanium nitride in said film preferably includes 26 wt% or less, more preferably 23 wt% or less of nitrogen moieties.
• said titanium nitride in the film includes 75 to 79 wt% (especially 76 to 78 wt%) titanium moieties and 21 to 25 wt% (especially 22 to 24 wt%) of nitrogen moieties.
• the film may be part of a building.
• Said film may have an area of at least 1 m 2 , preferably at least 5m 2 .
• Said film preferably defines a part of a roof, wall or window of a building.
• a method of making a film according to the first aspect comprising:
• Said polymeric material (A) of the second aspect may have any feature of polymeric material (A) of the first aspect.
• Said film of the second aspect may have any feature of the film of the first aspect.
• Said additive of the second aspect may have any feature of the additive of the first aspect.
• Said formulation (A) selected in step (i) may be a liquid formulation or a solid formulation, for example a masterbatch.
• Formulation (A) is preferably a solid masterbatch.
• Said formulation (A) of the second aspect may include at least l OOOppm or at least 2000ppm of said additive. It may include less than 20,000ppm of said additive.
• the wt% of said additive in said formulation (A) is greater than the wt% of said additive in the film made in the method.
• said formulation (A) may include at least 0.05 wt%, preferably at least 0.10 wt%, especially at least 0.15 wt% of said additive. It may include less than 2 wt% of said additive.
• Said formulation (A) is preferably a solid masterbatch.
• Said formulation (A) suitably includes a thermoplastic polymeric material.
• Formulation (A) suitably includes at least 90 wt%, preferably at least 95 wt%, especially at least 98 wt% of thermoplastic polymer.
• Said formulation (A) preferably includes a polymeric material (C) which is a fluoropolymer.
• Said polymeric material (C) is preferably a thermoplastic polymer. It is preferably saturated.
• Polymeric material (C) preferably includes a repeat unit (XI) which includes a moiety
• said repeat unit (XI) is an ethylene repeat unit.
• Said polymeric material (C) preferably includes a repeat unit (XII) which includes a moiety
• Said repeat unit (XI) may be a part of said repeat unit (XII).
• Said polymeric material (C) preferably includes a repeat unit (XIII) which includes a moiety
• X is a halogen atom, preferably selected from a chlorine and a fluorine atom.
• X represents a fluorine atom.
• Said polymeric material (C) preferably includes a repeat unit (XIV) which includes a moiety
• X is as described above.
• X represents a fluorine atom.
• Said polymeric material (C) is preferably a copolymer which includes a repeat unit of formula I and a repeat unit of formula III.
• the ratio of the mol% of moieties III divided by the mol% of moieties I is suitably in the range 0.25 to 4, preferably in the range 0.6 to 1 .5, more preferably in the range 0.9 to 1 .1
• Said polymeric material (C) may include at least 60 wt% of moieties of Formula III; and it may include less than 90 wt% of moieties of Formula III.
• Said polymeric material (C) may include at least 10 wt% of moieties of Formula I; and it may include less than 40 wt% of moieties of Formula I.
• Said polymeric material (C) may include at least 60 wt%, preferably at least 80 wt%, more preferably at least 95 wt%, especially at least 99 wt% of moieties of Formula IV.
• Said polymeric material polymer (C) may be ethylenechlorotrifluoroethylene (ECTFE) or an ethylene-tetrafluoroethylene copolymer (ETFE).
• ECTFE ethylenechlorotrifluoroethylene
• ETFE ethylene-tetrafluoroethylene copolymer
• Polymeric material (C) preferably has specific gravity, melt flow index, melting point, tensile strength, tensile modulus, tear propagation resistance and light transmission as described for said polymeric material (A).
• polymeric materials (A) and (C) are identical. They are preferably exactly the same polymeric material.
• melt-processing is suitably undertaken in an extruder and a film produced by standard techniques.
• a formulation (A) according to the second aspect comprising:
• Said polymeric material (C) of the third aspect may have any feature of polymeric material (C) of the second aspect.
• Said additive of the third aspect may have any feature of the additive of the first and/or second aspects.
• said liquid formulation (B) preferably at least 90 wt% of particles of said additive are present as primary particles - i.e. particles of said additive are generally not agglomerated.
• Said liquid formulation (B) may include at least 10 wt%, preferably at least 14 wt% of additive; it may include less than 50 wt% of said additive.
• Said liquid formulation (B) may include up to 90 wt%, for example up to 86 wt%, of carrier; and it suitably includes at least 50 wt% carrier.
• Said carrier is suitably a liquid (at 25°C and atmospheric pressure); it may be a vegetable or mineral oil or a glycol.
• a particularly preferred glycol is ethylene glycol.
• Said carrier may have a boiling point of less than the maximum temperature said polymeric material (C) is subjected to in step (iii) of the process.
• Said carrier may have a boiling point which is at least 10°C less than the maximum temperature said polymeric material (C) is subjected to in step (iii) of the process.
• Said carrier may have a boiling point of less than 330°C, preferably less than 320°C, more preferably less than 310°C, especially less than 250°C.
• liquid formulation (B) and polymeric material (C) may be contacted when both components are at a temperature of less than 50°C, for example at ambient temperature.
• Step (ii) suitably involves mixing liquid formulation (B) and polymeric material (C).
• melt-processing may be undertaken in an extruder.
• the maximum temperature to which liquid formulation (B) and polymeric material (C) are subjected in the extruder may be less than 330°C, for example less than 320°C.
• the maximum temperature may be less (e.g. by at least 10°C or at least 20°C) than the maximum temperature attained during extrusion in step (iii) of the method of the second aspect.
• carrier may be removed from the polymeric material in step (iii) or subsequent thereto. For example, carrier may be vented off during melt- processing.
• the method preferably comprises producing (and said formulation (A) preferably comprises) a solid, for example pellets, comprising said polymeric material (C) and said additive.
• Said solid preferably includes less than 5 wt%, for example less than 1 wt% of said carrier.
• said formulation (A) may be as described in the second aspect.
• a formulation (A) as described in the second and/or third aspects per se preferably comprises a polymeric material (C) which is a fluoropolymer and an additive selected from titanium nitride and tungsten oxide.
• Polymeric material (C) is preferably as described in the second aspect.
• Said additive, said titanium nitride and said tungsten oxide are preferably as described in the first, second and/or third aspects.
• said formulation (A) is in a solid (e.g. pellet) form and comprises particles of said additive comprising titanium nitride or tungsten oxide dispersed throughout said polymeric material (C).
• Said polymeric material (C) is preferably as described above and, more preferably, includes a structure of Formula IV. It is preferably an ethylene- tetrafluoroethylene copolymer (i.e. preferably an ETFE).
• Said formulation (A) preferably includes at least 0.05 wt%, especially at least 0.15 wt% of said additive and may include less than 2 wt% of said additive.
• Said formulation (A) preferably includes at least 90 wt%, more preferably at least 95 wt%, especially at least 98 wt% of polymeric material (C). It may include less than 99 wt% of polymeric material (C).
• Said part of the building may be a roof, wall or window of the building.
• the invention extends to the use of a film of the first aspect in or on a building for reducing the amount of IR radiation which passes into the building. Specific embodiments of the invention will now be described by way of example.
• Titanium nitride - refers to titanium nitride, with nanometer average primary particle sizes.
• Tungsten oxide - refers to particulate W0 2 .7 2 of less than 2 ⁇ .
• ETFE 6235 - refers to Dyneon (Trade Mark) ETFE which is a partially fluorinated copolymer comprising tetraflouroethylene and ethylene designed for film extrusion. It has a melting point of 266°C (DIN ES ISO 12086) and a Melt Flow Index of 10g/10mins (DIN EN ISO 1 133).
• the particle sizes described herein were examined using a Beckman Coulter LS230 Laser Diffraction Particle Size Analyzer, fitted with a Micro Volume Module filled with dichloromethane. The samples were pre-diluted in mineral oil before addition to the module.
• Examples 1 and 2 describe preparation of liquid formulations for use in preparing solid masterbatches; Examples 3 and 4 describe the preparation of solid masterbatches; Examples 5 to 10 describe preparation of films using the masterbatches; and Example 1 1 describe assessments undertaken on the films.
• Example 1 Preparation of liquid formulation comprising titanium nitride
• Titanium nitride (15 wt%) as described was slowly added with constant stirring to ethylene glycol (85 wt%). After the solid titanium nitride had been added, the mixer speed was increased to produce a smooth vortex and the speed of the mixer was maintained at the increased level until the solids had been fully dispersed. The dispersion was then transferred to a bead mill and milled until the titanium nitride had been milled to the desired particle size and agglomerates had been broken down. The particle size; measured by transmission electron microscopy (TEM) was 20nm.
• TEM transmission electron microscopy
• Milled Tungsten oxide 40 wt%) of particle size less than 2 ⁇ as described was slowly added with constant stirring as described in Example 1 to ethylene glycol (60 wt%) and the solids were fully dispersed as described in Example 1.
• the particle size, measured by Laser Diffraction was ⁇ 2 ⁇ .
• Example 3 Preparation of masterbatch comprising titanium nitride
• the liquid formulation of Example 1 (1 .28wt%) was blended with a mixture of dry polymer pellets of ETFE 6235 and C88AXMB powder to produce polymer/liquid IR absorber pre-mix.
• the blended composition was fed into a twin-screw extruder to melt the ETFE polymer and disperse particles of titanium nitride in the polymer matrix. Additionally, in the extruder, the ethylene glycol is vented off. On exit from the extruder, the composition is cooled and pelletised.
• Example C1 quoted in Table 1 is ETFE6235 in the absence of titanium nitride.
• Example 3 The procedure of Example 3 was generally followed by blending ETFE6235 (87.27 wt%), C88AXMB Ashai beads (9.18 wt%) and the liquid formulation of Example 2 (3.55 wt%). The output of the extruder was pelletized and the pelletised blend characterised as described in Example 3. Results are recorded in Table 1 . As for Example 3, oxide in the masterbatch makes the masterbatch darker compared to the original resin, but the MFI is substantially unaffected indicating that the carrier liquid has not plasticised the polymer or otherwise affected its rheology.
• Examples 5 to 10 - Preparation of films comprising masterbatches of Examples 3 and 4
• the masterbatches of Examples 3 and 4 were mixed with ETFE6235 polymer in various proportions and extruded using a single screw extruder fitted with a film die to produce films of 200 ⁇ thickness.
• the films produced (examples 5-10) were measured for transmittance using a UV-VIS-NIR spectrophotometer and the percentage reduction in IR transmittance measured at 700, 800, 900 and 1000nm to illustrate the reduction(%) in IR transmittance (i.e. IR absorption).
• the colours of the films produced was also measured and is reported as Lab* values (L*, a*, b* and ⁇ * compared to example C1). Results are provided in Table 3.
• Example 3 In comparison to the un-modified polymer materials (Example C5), it can be seen that by adding increasing quantities of the masterbatch Example 3 (i.e. Examples 5-7) that there is a reduction in the IR transmittance at the designated wavelengths and that this IR absorption effect increases as the quantity of the masterbatch of Example 3 is increased. Conversely as the IR absorbing effect increases the material does become darker but the transparency of the film is retained. Examples 8-10 based on the addition of the 5-7 with the exception that the IR absorbing effect is increased. Example 8-10 do become darker as the proportion of masterbatch of Example 4 is added but again the material transparency is retained.
• use of the masterbatches described allows films to be produced which, when used on the outside of buildings (e.g. as parts of roofs or walls), allow significant visible light transmission into the building whilst limiting IR transmission into the building.

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